JP5400041B2 - Agricultural surfactant composition and method for producing the same - Google Patents
Agricultural surfactant composition and method for producing the same Download PDFInfo
- Publication number
- JP5400041B2 JP5400041B2 JP2010513072A JP2010513072A JP5400041B2 JP 5400041 B2 JP5400041 B2 JP 5400041B2 JP 2010513072 A JP2010513072 A JP 2010513072A JP 2010513072 A JP2010513072 A JP 2010513072A JP 5400041 B2 JP5400041 B2 JP 5400041B2
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- Prior art keywords
- fatty acid
- mass
- alkyl ether
- polyoxyalkylene alkyl
- added
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 44
- 239000004094 surface-active agent Substances 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 89
- 239000000194 fatty acid Substances 0.000 claims description 89
- 229930195729 fatty acid Natural products 0.000 claims description 89
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 66
- 150000004665 fatty acids Chemical class 0.000 claims description 62
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 59
- 239000003905 agrochemical Substances 0.000 claims description 54
- 150000005215 alkyl ethers Chemical class 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000003054 catalyst Substances 0.000 claims description 33
- 125000002947 alkylene group Chemical group 0.000 claims description 26
- -1 polyoxy Polymers 0.000 claims description 25
- 238000004821 distillation Methods 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000012644 addition polymerization Methods 0.000 claims description 13
- 238000005809 transesterification reaction Methods 0.000 claims description 13
- 230000032050 esterification Effects 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 150000004670 unsaturated fatty acids Chemical group 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims 5
- 150000002148 esters Chemical class 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 238000007259 addition reaction Methods 0.000 description 29
- 239000000543 intermediate Substances 0.000 description 29
- 239000007788 liquid Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 17
- 239000006260 foam Substances 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 230000000149 penetrating effect Effects 0.000 description 15
- 238000005187 foaming Methods 0.000 description 14
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- 230000007480 spreading Effects 0.000 description 13
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- 239000002904 solvent Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 231100000674 Phytotoxicity Toxicity 0.000 description 9
- 150000004703 alkoxides Chemical class 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
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- 239000000395 magnesium oxide Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
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- 229910000000 metal hydroxide Inorganic materials 0.000 description 8
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- 241000251468 Actinopterygii Species 0.000 description 7
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- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 7
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 7
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- 230000001988 toxicity Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
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- 239000000047 product Substances 0.000 description 6
- 239000012085 test solution Substances 0.000 description 6
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- 239000002540 palm oil Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000003381 solubilizing effect Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 241000270295 Serpentes Species 0.000 description 3
- 240000004429 Tephrosia purpurea Species 0.000 description 3
- 235000017517 Tephrosia purpurea Nutrition 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229940035429 isobutyl alcohol Drugs 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VACHUYIREGFMSP-UHFFFAOYSA-N 9,10-dihydroxyoctadecanoic acid Chemical compound CCCCCCCCC(O)C(O)CCCCCCCC(O)=O VACHUYIREGFMSP-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000000895 acaricidal effect Effects 0.000 description 2
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- 239000002253 acid Substances 0.000 description 2
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
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- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 2
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- 238000009835 boiling Methods 0.000 description 1
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OTNVFHCIZYJHGW-UHFFFAOYSA-N lanthanum(3+) tris(trifluoromethyl)sulfanium Chemical compound FC(F)(F)[S+](C(F)(F)F)C(F)(F)F.[La+3] OTNVFHCIZYJHGW-UHFFFAOYSA-N 0.000 description 1
- SORGMJIXNUWMMR-UHFFFAOYSA-N lanthanum(3+);propan-2-olate Chemical compound [La+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SORGMJIXNUWMMR-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- RDSLSIIVSGZAGJ-USRGLUTNSA-N octadec-11-enoic acid;(e)-octadec-11-enoic acid Chemical compound CCCCCCC=CCCCCCCCCCC(O)=O.CCCCCC\C=C\CCCCCCCCCC(O)=O RDSLSIIVSGZAGJ-USRGLUTNSA-N 0.000 description 1
- KQJBQMSCFSJABN-UHFFFAOYSA-N octadecan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-].CCCCCCCCCCCCCCCCCC[O-] KQJBQMSCFSJABN-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- SECPZKHBENQXJG-BQYQJAHWSA-N palmitelaidic acid Chemical compound CCCCCC\C=C\CCCCCCCC(O)=O SECPZKHBENQXJG-BQYQJAHWSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000011888 snacks Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XQKBFQXWZCFNFF-UHFFFAOYSA-K triiodosamarium Chemical compound I[Sm](I)I XQKBFQXWZCFNFF-UHFFFAOYSA-K 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Toxicology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、農薬の乳化剤、分散剤、展着剤、機能性展着剤(アジュバンド)及び水和剤の用途に適する農薬用界面活性剤組成物に関する。 The present invention relates to an agrochemical surfactant composition suitable for use as an emulsifier, dispersant, spreader, functional spreader (adjuvant) and wettable powder.
殺菌剤、殺虫剤、殺ダニ剤、除草剤及び植物成長調節剤等の農薬は、農薬の効果を充分に引き出すため、農薬の散布時の作業効率もしくは安全性等の面から適切な剤型が選択される。これらのうち、農薬の乳化分散液などは万遍なく散布対象に対して均一に付着することが期待され、使用されており、一般に油性のものが多い農薬の水への分散のために、各種界面活性剤が使用される。 Pesticides such as fungicides, insecticides, acaricides, herbicides, and plant growth regulators have the appropriate dosage form in terms of work efficiency or safety when spraying the pesticides in order to fully exploit the effects of the pesticides. Selected. Of these, emulsified dispersions of agricultural chemicals are expected to be uniformly applied to the object to be dispersed and are used, and in order to disperse the agricultural chemicals that are generally oily in water, A surfactant is used.
また、植物の葉、茎及び昆虫などの表皮面は液体のぬれを反撥する成分又は構造をもっている。例えば植物の表面にはロウリポイド類が分泌されていたり、羽毛状の繊維が密生していたり、あるいは表面に微細な凹凸があることが多く、害虫の表面にもケラチン質と同様の層があり、いずれも農薬の水分散液をはじく性質を有している。このため散布した農薬も十分効果をあげることができないことがあり、散布した農薬に湿潤、浸透、拡展、固着などの諸性質を強めて薬効を増加せしめるための展着剤及び機能性展着剤(アジュバンド)が使用される。 In addition, the skin surface of plants such as leaves, stems and insects has a component or structure that repels liquid wetting. For example, low lipoids are secreted on the surface of plants, feather-like fibers are dense, or there are many fine irregularities on the surface, and there are layers similar to keratin on the surface of pests, Both have the property of repelling aqueous dispersions of agricultural chemicals. For this reason, sprayed pesticides may not be effective enough, and spreaders and functional spreads are used to increase the efficacy of the sprayed pesticides by increasing their properties such as wetting, penetration, spreading, and sticking. An agent (adjuband) is used.
これら農薬用界面活性剤としては、従来より各種アルキレンオキシド付加型の非イオン性界面活性剤が知られている。例えば、特許文献1には特定の脂肪酸ポリオキシアルキレンアルキルエーテルからなるエステル型非イオン性界面活性剤を含有する農薬用展着剤が記載されている。また、特許文献2には低温安定性に優れた界面活性剤組成物である農薬用展着剤組成物が開示されている。 As these agrochemical surfactants, various alkylene oxide addition type nonionic surfactants have been known. For example, Patent Document 1 describes a spreading agent for agricultural chemicals containing an ester-type nonionic surfactant made of a specific fatty acid polyoxyalkylene alkyl ether. Patent Document 2 discloses a spreading agent composition for agricultural chemicals which is a surfactant composition having excellent low-temperature stability.
また、一般に、非イオン性界面活性剤からなる農薬用界面活性剤は、液状物の農薬製剤とするために使用され、あるいは、液状物である農薬用展着剤として、液状物である農薬製剤に配合されることが多い。そのため実使用においては、油性である農薬成分の可溶化力や、タンクでの予備配合、農薬散布時の作業性及び河川での発泡(汚染)抑制のための低泡性と破泡性、植物表面等への浸透性などの基本性能と共に、使用時、低温保存時、低温から常温へ温度が変化した際に成分の析出、分離の起こらない安定性が求められる。 In general, an agrochemical surfactant comprising a nonionic surfactant is used to form a liquid agrochemical formulation, or a liquid agrochemical formulation as a liquid agrochemical spreader. It is often blended with. Therefore, in actual use, low foaming and foam breaking properties for solubilizing power of oily pesticide ingredients, pre-mixing in tanks, workability when spraying pesticides and suppressing foaming (contamination) in rivers, plants In addition to basic performance such as permeability to the surface, stability that does not cause precipitation or separation of components when the temperature changes from low temperature to room temperature during use or storage at low temperatures is required.
本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、農薬用界面活性剤として界面活性(可溶化力、分散力、浸透力、低泡性、破泡性)に優れるとともに、低温安定性に優れ、さらに生分解性が良好で、環境安全性(植物薬害、魚毒性)に優れた農薬用界面活性剤組成物を提供することを目的とする。 An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention is excellent in surfactant activity (solubilizing power, dispersing power, penetrating power, low foaming property, foam breaking property) as an agrochemical surfactant, excellent in low temperature stability, and in good biodegradability. An object of the present invention is to provide an agrochemical surfactant composition excellent in environmental safety (phytotoxicity, fish toxicity).
前記課題を解決するための手段としては、以下の通りである。即ち、
<1> 下記一般式(I)で表され、下記式(A)で表されるナロー率が55質量%以上である脂肪酸ポリオキシアルキレンアルキルエーテルを含有することを特徴とする農薬用界面活性剤組成物である。
<1> A surfactant for agricultural chemicals comprising a fatty acid polyoxyalkylene alkyl ether represented by the following general formula (I) and having a narrow ratio represented by the following formula (A) of 55% by mass or more. It is a composition.
(ただし、前記式(A)中、iは、アルキレンオキシドの付加モル数(EOとPOの合計の付加モル数)を示し、nMAXは、前記一般式(I)で示される物質全体の中でアルキレンオキシドの付加モル数が質量基準で最も多く存在するもののiの値を示す。Yiは、全体の脂肪酸ポリオキシアルキレンアルキルエーテル中に存在するアルキレンオキシドの付加モル数がiである脂肪酸ポリオキシアルキレンアルキルエーテルの割合(質量%)を示す。)
<2> 前記<1>に記載の脂肪酸ポリオキシアルキレンアルキルエーテルと、水と、炭素数1〜4である低級アルコールとを含み、前記脂肪酸ポリオキシアルキレンアルキルエーテル/前記水/前記低級アルコールで表される含有量の比率が、10質量%〜60質量%/10質量%〜70質量%/10質量%〜70質量%であることを特徴とする農薬用界面活性剤組成物である。 (In the formula (A), i represents the number of added moles of alkylene oxide (total number of added moles of EO and PO), and n MAX represents the total number of substances represented by the general formula (I). And i represents the value of the number of added moles of alkylene oxide present on the mass basis, and Yi represents a fatty acid polyoxy having an added number of moles of alkylene oxide present in the whole fatty acid polyoxyalkylene alkyl ether. (The ratio (% by mass) of the alkylene alkyl ether is shown.)
<2> The fatty acid polyoxyalkylene alkyl ether according to <1>, water, and a lower alcohol having 1 to 4 carbon atoms, represented by the fatty acid polyoxyalkylene alkyl ether / the water / the lower alcohol. It is a surfactant composition for agricultural chemicals, wherein the content ratio is 10% by mass to 60% by mass / 10% by mass to 70% by mass / 10% by mass to 70% by mass.
本発明によれば、従来における前記諸問題を解決し、前記目的を達成することができ、本発明は、農薬用界面活性剤としての界面活性(可溶化力、分散力、浸透力、低泡性、破泡性)に優れるとともに、低温安定性に優れ、さらに生分解性が良好で、環境安全性(植物薬害、魚毒性)に優れる農薬用海面活性剤組成物を提供することができる。 According to the present invention, the above-described problems can be solved and the object can be achieved. The present invention is a surface active agent (solubilizing power, dispersing power, penetrating power, low foaming) as a surfactant for agricultural chemicals. It is possible to provide a sea surface active agent composition for agricultural chemicals that is excellent in low-temperature stability, biodegradability, and environmental safety (phytotoxicity, fish toxicity).
本発明で用いられる脂肪酸ポリオキシアルキレンアルキルエーテルからなるエステル型非イオン性界面活性剤は、下記一般式(I)で表され、下記式(A)で表されるナロー率が55質量%以上である脂肪酸ポリオキシアルキレンアルキルエーテルである。
(ただし、前記式(A)中、iは、アルキレンオキシドの付加モル数(EOとPOの合計の付加モル数)を示し、nMAXは、前記一般式(I)で示される物質全体の中でアルキレンオキシドの付加モル数が質量基準で最も多く存在するもののiの値を示す。Yiは、全体の脂肪酸ポリオキシアルキレンアルキルエーテル中に存在するアルキレンオキシドの付加モル数がiである脂肪酸ポリオキシアルキレンアルキルエーテルの割合(質量%)を示す。) (In the formula (A), i represents the number of added moles of alkylene oxide (total number of added moles of EO and PO), and n MAX represents the total number of substances represented by the general formula (I). And i represents the value of the number of added moles of alkylene oxide present on the mass basis, and Yi represents a fatty acid polyoxy having an added number of moles of alkylene oxide present in the whole fatty acid polyoxyalkylene alkyl ether. (The ratio (% by mass) of the alkylene alkyl ether is shown.)
脂肪酸残基R1COの炭素数が14以上あるいは22以下であると、表面張力、浸透力、低泡性等の界面活性や、植物薬害、魚毒など環境安全性が良好となる。R1COの炭素数を16〜18とすることにより、いっそう界面活性と環境安全性に優れる。
前記脂肪酸残基R1COは、ミリスチン酸、5−メチルテトラデカン酸、2,2−ジメチルテトラデカン酸、ペンタデカン酸、パルミチン酸、ソーマリン酸(9−ヘキサデセン酸)、マーガリン酸、ステアリン酸、オレイン酸、バクセン酸(11−オクタデセン酸)、リノール酸、リノレン酸、リシノール酸(ひまし油)、9,10−ジヒドロキシオクタデカン酸(ひまし油)、エライジン酸、イソステアリン酸などから導入することができる。このように、前記脂肪酸残基R1COは、ヒドロキシル基等の置換基を有していてもよい。
また、前記脂肪酸残基R1COは、前記置換基を有する化合物の混合物から導入することもでき、大豆油、菜種油、パーム油などの植物油由来の組成分布を有する脂肪酸などからも導入することができる。特に、パーム油は、植物油として最も生産量が多く安定供給が可能である。また、パーム油由来の脂肪酸は大豆油や菜種油よりも酸化安定性に優れる点でよい。When the carbon number of the fatty acid residue R 1 CO is 14 or more or 22 or less, surface activity such as surface tension, penetrating power, low foaming property, and environmental safety such as plant phytotoxicity and fish poison are improved. By setting the carbon number of R 1 CO to 16-18, the surface activity and environmental safety are further improved.
The fatty acid residue R 1 CO includes myristic acid, 5-methyltetradecanoic acid, 2,2-dimethyltetradecanoic acid, pentadecanoic acid, palmitic acid, thamarinic acid (9-hexadecenoic acid), margaric acid, stearic acid, oleic acid, It can be introduced from vaccenic acid (11-octadecenoic acid), linoleic acid, linolenic acid, ricinoleic acid (castor oil), 9,10-dihydroxyoctadecanoic acid (castor oil), elaidic acid, isostearic acid and the like. Thus, the fatty acid residue R 1 CO may have a substituent such as a hydroxyl group.
The fatty acid residue R 1 CO can also be introduced from a mixture of compounds having the substituent, and can also be introduced from fatty acids having a composition distribution derived from vegetable oils such as soybean oil, rapeseed oil, and palm oil. it can. In particular, palm oil has the highest production amount as a vegetable oil and can be stably supplied. Moreover, the fatty acid derived from palm oil may be excellent in oxidation stability as compared with soybean oil or rapeseed oil.
前記脂肪酸残基R1COとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、低温安定性の観点から炭素鎖中にオレイン酸、リノール酸、リノレン酸などの不飽和結合を有する脂肪酸残基が好ましく、特に脂肪酸残基R1COに対応する脂肪酸メチルエステルとしたときのヨウ素価が60〜150のものが低温安定性の点で好ましく、さらに、70〜130であるものがより好ましい。また、酸化安定性の面からは70〜110が特に好ましい。具体的には、パーム油由来の脂肪酸メチルエステルであるライオン製パステルM181及びM182が挙げられる。The fatty acid residue R 1 CO is not particularly limited and may be appropriately selected depending on the intended purpose. For example, unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid are included in the carbon chain from the viewpoint of low temperature stability. Fatty acid residues having a bond are preferable, and those having an iodine value of 60 to 150, particularly when the fatty acid methyl ester corresponding to the fatty acid residue R 1 CO is used are preferable in terms of low-temperature stability, and more preferably 70 to 130. Those are more preferred. Moreover, 70-110 are especially preferable from the surface of oxidation stability. Specific examples include Lion pastels M181 and M182, which are fatty acid methyl esters derived from palm oil.
低級アルキル基R2の炭素数としては、特に制限はないが、1〜3であり、1〜2が好ましく、製造のしやすさという点で、炭素数1のメチル基が特に好ましい。
前記低級アルキル基R2の炭素数が4以上となると魚毒及び植物薬害性が悪くなることがあり、5以上となると更に浸透性も低下する。また、R2が水素の場合は、浸透性が著しく悪く、展着剤としての性能が低下する。The number of carbon atoms of the lower alkyl group R 2, is not particularly limited, is 1-3, preferably 1-2, in terms of ease of manufacture, particularly preferably a methyl group having one carbon atom.
When the number of carbon atoms of the lower alkyl group R 2 is 4 or more, fish poison and phytotoxicity may be deteriorated, and when it is 5 or more, the permeability is further lowered. Further, when R 2 is hydrogen, the permeability is remarkably poor, and the performance as a spreading agent is lowered.
エチレンオキシド(EO)の平均付加モル数mの値としては、2〜10であり、3〜7が好ましい。該平均付加モル数がこの値より小さい場合は、著しく浸透力が低下し、一方、大きい場合は、浸透力が低下するとともに起泡性が高くなりすぎる。浸透力及び起泡力の点で平均付加モル数は3〜7が好ましい。
プロピレンオキシド(PO)の平均付加モル数nの値としては、1〜4であり、2〜4が好ましい。該平均付加モル数nが5以上となると液安定性が低下する。付加モル数が0になると浸透力が低下する。
前記EOとPOの付加モル数の組み合わせは、EO3〜7モル・PO2〜4モルが浸透力、低泡性、液安定性及び(魚毒)安全性の面で好ましい。
前記EOとPOの付加形態としては、ブロック付加であり、付加順序は前記一般式(I)に示される通り、POが末端(−OR2側)に付加したものである必要がある。
前記付加形態がブロック付加で且つ、POが末端に付加したものとすることで、低泡性で、浸透力に優れ、低温安定性にも優れたものとなる。また、魚毒性などの環境安全性にも優れたものとなる。一方、付加形態がEOとPOがランダムに付加したものとすると浸透力に劣り、低温安定性にも劣るものとなることがある。また、POが末端ではなく脂肪酸残機R1CO側に付加したものでは低泡性の点で劣るものとなる。The average added mole number m of ethylene oxide (EO) is 2 to 10, preferably 3 to 7. When the average added mole number is smaller than this value, the penetrating power is remarkably lowered. On the other hand, when the average added mole number is large, the penetrating power is lowered and the foamability is too high. The average added mole number is preferably 3 to 7 in terms of penetrating power and foaming power.
The average added mole number n of propylene oxide (PO) is 1 to 4, preferably 2 to 4. When the average added mole number n is 5 or more, the liquid stability decreases. When the number of added moles becomes zero, the penetrating power decreases.
The combination of the number of added moles of EO and PO is preferably 3 to 7 moles of EO and 2 to 4 moles of PO in terms of penetrating power, low foamability, liquid stability, and (fish poison) safety.
The addition form of EO and PO is block addition, and the addition order needs to be that PO is added to the terminal (-OR 2 side) as shown in the general formula (I).
When the addition form is a block addition and PO is added to the terminal, the foam has low foaming properties, excellent penetrating power, and excellent low-temperature stability. In addition, it is excellent in environmental safety such as fish toxicity. On the other hand, if EO and PO are added randomly, the penetrating power is inferior and the low-temperature stability may be inferior. Moreover, when PO is added to the fatty acid residue R 1 CO side instead of the terminal, it is inferior in terms of low foamability.
前記脂肪酸ポリオキシアルキレンアルキルエーテルとしては、特に制限はなく、目的に応じて適宜選択することができ、様々なアルキレンオキシドの付加モル数を有するアルキレンオキシド付加体の混合物であってよく、その場合、前記式(A)のナロー率で規定される特定の付加モル数分布を有する必要がある。
前記式(A)のナロー率としては、最も質量%の多いアルキレンオキシドの付加モル数を有する付加体のアルキレンオキシドの付加モル数をnMAXとしたとき、その±2の付加モル数のものの総和を示す。
ここでアルキレンオキシドの付加モル数は、EOとPOの合計の付加モル数であり、同じアルキレンオキシドの付加モル数を有するものには、EO、POの各々の付加モル数は異なるが合計量は同じである複数のアルキレンオキシド付加体を含む。The fatty acid polyoxyalkylene alkyl ether is not particularly limited and may be appropriately selected depending on the purpose, and may be a mixture of alkylene oxide adducts having various addition moles of alkylene oxide. It is necessary to have a specific added mole number distribution defined by the narrow ratio of the formula (A).
The narrow ratio of the formula (A) is the sum of the addition mole number of ± 2 when the addition mole number of the alkylene oxide of the adduct having the most addition mole number of alkylene oxide of the mass% is n MAX. Indicates.
The number of added moles of alkylene oxide is the total number of added moles of EO and PO. For those having the same number of added moles of alkylene oxide, the number of added moles of EO and PO is different, but the total amount is Includes multiple alkylene oxide adducts that are the same.
前記式(A)のナロー率としては、55質量%以上であり、60質量%以上が好ましく、65質量%以上がより好ましい。前記ナロー率は、高いほど好ましいが、高くなるほど、固体触媒を使用した場合に、反応終了後の触媒ろ過速度の低下による製造時間の延長による生産性の低下によって製造コストが高くなり、また、アルカリ触媒を使用した場合に、蒸留による歩留りの低下に基づく生産性の低下により製造コストが高くなる。上限値としては、実質的には95質量%以下である。前記ナロー率を55質量%以上とすることにより低泡性で、破泡性、液安定性に優れたものとなる。 As a narrow rate of said Formula (A), it is 55 mass% or more, 60 mass% or more is preferable and 65 mass% or more is more preferable. The higher the narrow rate, the more preferable, but the higher the rate, the higher the manufacturing cost due to the decrease in productivity due to the extension of the manufacturing time due to the decrease in the catalyst filtration rate after the completion of the reaction. When a catalyst is used, the manufacturing cost is increased due to a decrease in productivity due to a decrease in yield due to distillation. As an upper limit, it is 95 mass% or less substantially. By setting the narrow ratio to 55% by mass or more, the foam has low foaming properties and excellent foam breaking properties and liquid stability.
前記ナロー率としては、前記一般式(I)で表される脂肪酸ポリオキシアルキレンアルキルエーテルの製造方法等によって制御することができる。
前記脂肪酸ポリオキシアルキレンアルキルエーテルの製造方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、複合金属酸化物触媒を用いて、脂肪酸アルキルエステルにPOとEOをブロック付加重合させる方法(特開2000−144179号公報参照)や、前記R2Oに相当する低級アルコールに同様に複合金属酸化物触媒を用いてブロック付加重合(特開平9−262456号公報参照)した後に、対応する脂肪酸エステルとエステル交換あるいは対応する脂肪酸とエステル化を行う方法や、さらには前記低級アルコールにアルカリ触媒を用いてPOとEOをブロック付加重合を行った後、適宜未反応の低級アルコールや低付加モル数成分を蒸留除去することで所望のナロー率となるように付加モル数分布を制御した後、対応する脂肪酸エステルとエステル交換あるいは対応する脂肪酸とエステル化を行う方法などが挙げられる。The narrow rate can be controlled by the production method of the fatty acid polyoxyalkylene alkyl ether represented by the general formula (I).
The method for producing the fatty acid polyoxyalkylene alkyl ether is not particularly limited and may be appropriately selected depending on the intended purpose. For example, PO and EO are added to the fatty acid alkyl ester by block using a composite metal oxide catalyst. After polymerization (see JP-A No. 2000-144179) or block addition polymerization (see JP-A No. 9-262456) using a mixed metal oxide catalyst in the same manner as the lower alcohol corresponding to R 2 O. A method of transesterification with the corresponding fatty acid ester or esterification with the corresponding fatty acid, and further, after block addition polymerization of PO and EO using an alkali catalyst to the lower alcohol, an unreacted lower alcohol or The number of moles added is reduced to the desired narrow ratio by distilling off the low added moles component. After control, a method of performing the corresponding fatty acid ester and a transesterification or the corresponding fatty acid and esterifying the like.
前記脂肪酸ポリオキシアルキレンアルキルエーテルの製造を対応する脂肪酸アルキルエステルへのPOとEOのブロック付加重合により行う場合、用いる触媒としては、特に制限はないが、蒸留等の他の精製手段を要さずに、所望のナロー率を有する脂肪酸ポリオキシアルキレンアルキルエーテルを得ることができることから、金属水酸化物及び/又は金属アルコキシド等により表面改質されたハイドロタルサイトの焼成物触媒など、アルカリにより表面改質された金属イオン(Al3+、Ga3+、In3+、Tl3+、Co3+、Sc3+、La3+、Mn2+等)が添加された酸化マグネシウム等の複合金属酸化物触媒が好ましい。When the production of the fatty acid polyoxyalkylene alkyl ether is carried out by block addition polymerization of PO and EO to the corresponding fatty acid alkyl ester, the catalyst used is not particularly limited, but does not require other purification means such as distillation. In addition, since a fatty acid polyoxyalkylene alkyl ether having a desired narrow ratio can be obtained, surface modification with an alkali such as a calcined catalyst of hydrotalcite modified with a metal hydroxide and / or a metal alkoxide or the like is possible. Preferred is a composite metal oxide catalyst such as magnesium oxide to which refined metal ions (Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 3+ , Sc 3+ , La 3+ , Mn 2+, etc.) are added.
このような触媒としては、例えば下記一般式(2)で表される水酸化アルミニウムと水酸化マグネシウムの共沈物を、焼成することにより得ることができるアルミナ・マグネシア複合酸化物を金属水酸化物または金属アルコキシドで表面改質した触媒が具体的に挙げられる。
nMgO・Al2O3・mH2O・・・(2)
(ただし、前記式(2)中、nは、特に限定されないが、2.5前後が好適であり、mは、特に限定されない)
共沈物の焼成温度としては、400℃〜950℃が好ましく、より好ましくは500℃〜750℃である。As such a catalyst, for example, an alumina-magnesia composite oxide that can be obtained by firing a coprecipitate of aluminum hydroxide and magnesium hydroxide represented by the following general formula (2) is used as a metal hydroxide. Or the catalyst surface-modified with the metal alkoxide is specifically mentioned.
nMgO · Al 2 O 3 · mH 2 O (2)
(However, in the formula (2), n is not particularly limited, but is preferably around 2.5, and m is not particularly limited.)
As a baking temperature of a coprecipitate, 400 to 950 degreeC is preferable, More preferably, it is 500 to 750 degreeC.
前記改質に用いる金属水酸化物としては、特に制限はなく、目的に応じて適宜選択することができるが、アルカリ金属又はアルカリ土類金属の水酸化物が好ましく、水酸化ナトリウム、水酸化カリウムがより好ましい。
前記金属アルコキシドとしては、特に制限はなく、目的に応じて適宜選択することができるが、アルカリ金属、アルカリ土類金属が好ましく、ナトリウムアルコキシド、カリウムアルコキシドがより好ましい。There is no restriction | limiting in particular as a metal hydroxide used for the said modification | reformation, Although it can select suitably according to the objective, The hydroxide of an alkali metal or an alkaline-earth metal is preferable, sodium hydroxide, potassium hydroxide Is more preferable.
There is no restriction | limiting in particular as said metal alkoxide, Although it can select suitably according to the objective, An alkali metal and alkaline-earth metal are preferable and sodium alkoxide and potassium alkoxide are more preferable.
前記改質触媒の製造方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、焼成アルミナ・マグネシア複合酸化物をアルカリ金属、アルカリ土類金属の水酸化物又はアルコキシドで予め改質した後、反応用触媒として使用する方法と、アルコキシル化用反応器の中で、原料の脂肪酸アルキルエステル中に焼成アルミナ・マグネシア複合酸化物と金属水酸化物又は金属アルコキシドを混合し、脂肪酸アルキルエステルの中で触媒の改質をした後、アルキレンオキシドとの反応を行う方法がある。
前者の方法としては、特に限定はないが、前記焼成アルミナ・マグネシア複合酸化物に前記金属水酸化物、金属アルコキシドの水溶液又はアルコール溶液を噴霧した後、乾燥あるいは焼成する方法が好ましい。
また、後者の方法においては、特に制限はないが、原料脂肪酸アルキルエステルへの前記焼成アルミナ・マグネシア複合酸化物と前記金属水酸化物又は金属アルコキシドの添加順序は、特に限定されない。この際、前記金属水酸化物又は金属アルコキシドを低級アルコール又は水溶液として添加することも、触媒表面酸点をより均質に、かつより選択的に部分改質する意味で好ましい。
前記焼成アルミナ・マグネシア複合酸化物の改質に使用する金属水酸化物又は金属アルコキシドの量としては、特に制限はないが、焼成アルミナ・マグネシア複合酸化物に対して1質量%〜20質量%が好ましい。The method for producing the reforming catalyst is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the calcined alumina / magnesia composite oxide may be an alkali metal, alkaline earth metal hydroxide or alkoxide. After reforming in advance, in a method for use as a reaction catalyst and in a reactor for alkoxylation, a calcined alumina / magnesia composite oxide and a metal hydroxide or a metal alkoxide are mixed in a raw material fatty acid alkyl ester, There is a method of performing a reaction with an alkylene oxide after modifying a catalyst in a fatty acid alkyl ester.
The former method is not particularly limited, but a method of spraying the metal hydroxide, an aqueous solution of metal alkoxide or an alcohol solution on the calcined alumina / magnesia composite oxide and then drying or calcining is preferable.
In the latter method, the order of addition of the calcined alumina / magnesia composite oxide and the metal hydroxide or metal alkoxide to the raw material fatty acid alkyl ester is not particularly limited. At this time, it is also preferable to add the metal hydroxide or metal alkoxide as a lower alcohol or an aqueous solution in the sense that the surface acid point of the catalyst is more uniformly and more selectively partially modified.
The amount of the metal hydroxide or metal alkoxide used for the modification of the calcined alumina / magnesia composite oxide is not particularly limited, but is 1% by mass to 20% by mass with respect to the calcined alumina / magnesia composite oxide. preferable.
前記表面改質を行わない場合は、ブロック付加反応生成物としては所望のナロー率のものを得ることが出来ない場合もあるが、その場合はEOとPOの付加モル数の少ない成分を蒸留等の操作により除去することで所望のナロー率としてもよい。なお、POを末端に挿入するためには、ブロック付加重合をPO、EOの順で行う必要がある。 When the surface modification is not performed, it may not be possible to obtain a block addition reaction product having a desired narrow ratio. In such a case, components having a small number of added moles of EO and PO are distilled. It is good also as a desired narrow rate by removing by operation of. In order to insert PO at the end, it is necessary to perform block addition polymerization in the order of PO and EO.
前記脂肪酸ポリオキシアルキレンアルキルエーテルの製造を前記R2Oに相当する低級アルコールに対して、同様に前記複合金属酸化物触媒を用いてブロック付加重合した後、対応する脂肪酸エステルとエステル交換あるいは対応する脂肪酸とエステル化を行う方法により行う場合、前記複合金属酸化物触媒としては、特に制限はないが、前記と同様のものを使用することができ、また、前記複合金属酸化物触媒は、前記表面改質を行ってもよいが、低級アルコールへの付加反応の場合は表面改質を行わなくても所望のナロー率を得ることができる。In the production of the fatty acid polyoxyalkylene alkyl ether, the lower alcohol corresponding to the R 2 O is similarly subjected to block addition polymerization using the composite metal oxide catalyst, and then transesterified with or corresponding to the corresponding fatty acid ester. In the case of performing the esterification with a fatty acid, the composite metal oxide catalyst is not particularly limited, but the same one as described above can be used, and the composite metal oxide catalyst is formed on the surface. Although modification may be performed, in the case of addition reaction to a lower alcohol, a desired narrow ratio can be obtained without performing surface modification.
前記固体触媒によるエチレンオキシドとプロピレンオキシドの付加反応は常法により行うことができる。例えば反応温度としては、特に制限はないが、80℃〜230℃であり、120℃〜190℃が好ましい。また、反応圧力としては、反応温度にもよるが、0〜0.8MPaであり、0.2MPa〜0.5MPa(ゲージ圧)が好ましい。
前記触媒の使用量としては、反応に供されるアルキレンオキシドと脂肪酸アルキルエステルとのモル比によっても変わるが、通常は脂肪酸アルキルエステル量に対して0.1質量%〜20質量%が好ましい。The addition reaction of ethylene oxide and propylene oxide with the solid catalyst can be performed by a conventional method. For example, although there is no restriction | limiting in particular as reaction temperature, it is 80 to 230 degreeC, and 120 to 190 degreeC is preferable. The reaction pressure is 0 to 0.8 MPa, preferably 0.2 MPa to 0.5 MPa (gauge pressure), although it depends on the reaction temperature.
The amount of the catalyst used varies depending on the molar ratio of alkylene oxide and fatty acid alkyl ester to be used in the reaction, but is usually preferably 0.1% by mass to 20% by mass with respect to the amount of fatty acid alkyl ester.
前記脂肪酸ポリオキシアルキレンアルキルエーテルの製造を前記R2Oに相当する低級アルコールにNaOHなどのアルカリ触媒を用いてブロック付加重合した後、対応する脂肪酸エステルとエステル交換あるいは対応する脂肪酸とエステル化を行う方法により行う場合、付加反応のみでは所望のナロー率のものを得ることができない。In the production of the fatty acid polyoxyalkylene alkyl ether, the lower alcohol corresponding to the R 2 O is subjected to block addition polymerization using an alkali catalyst such as NaOH, and then transesterified with the corresponding fatty acid ester or esterified with the corresponding fatty acid. When the method is used, a desired narrow ratio cannot be obtained only by the addition reaction.
本方法で、末端にPO単位を有するブロック付加体を最終的に得るためには、まずPOの付加反応を行い、続いてEOの付加反応を行う必要がある。
この場合、所望のナロー率を得る方法としては、POとEOの付加反応終了後に得られた中間体から未反応原料や低付加モル体を蒸留等により除去する方法が挙げられる。蒸留により未反応原料等を除去する場合は、減圧蒸留等の常法で行うことができ、未反応原料を脂肪酸ポリオキシアルキレンアルキルエーテル中、2.5質量%以下とすることが、浸透力や液安定性の点で好ましい。In order to finally obtain a block adduct having a PO unit at the terminal by this method, it is necessary to first carry out an addition reaction of PO and then an addition reaction of EO.
In this case, as a method for obtaining a desired narrow ratio, a method of removing unreacted raw materials and low addition moles from the intermediate obtained after completion of the addition reaction of PO and EO by distillation or the like can be mentioned. When removing unreacted raw materials by distillation, it can be carried out by a conventional method such as distillation under reduced pressure, and the unreacted raw materials in the fatty acid polyoxyalkylene alkyl ether should be 2.5% by mass or less. It is preferable in terms of liquid stability.
また、POの付加反応を行って得た中間体1から蒸留により未反応分や低付加モル体を除去する方法や、さらに続けてEOの付加反応を行って得たブロック付加体(中間体2)からも再度蒸留等により低付加モル体を除去する方法も、POとEO各々の付加モル数分布を別個に制御でき、より狭い付加モル数分布を有するブロック付加体を容易に得ることができる点でより好ましい。 Further, a method of removing unreacted components and low-addition moles by distillation from the intermediate 1 obtained by the PO addition reaction, and a block adduct (intermediate 2) obtained by the subsequent EO addition reaction. ) Also removes low addition moles by distillation or the like, and the addition mole number distribution of PO and EO can be controlled separately, and a block adduct having a narrower addition mole number distribution can be easily obtained. More preferable in terms.
この場合、中間体1について前記式(A)に準じてナロー率を計算したときのナロー率としては、40質量%以上が浸透力や液安定性の点で好ましく、50質量%以上がより好ましく、55質量%以上が特に好ましい。また、未反応の原料アルコールの残存量としては、全脂肪酸ポリオキシアルキレンアルキルエーテル中、2.5質量%以下であることが浸透力や液安定性の点で好ましく、1.0質量%以下がより好ましい。
このようなナロー率の高いPO付加体としては、特に制限はなく、トリプロピレングリコールモノメチルエーテル(例えば商品名メチルプロピレントリグリコール(MFTG)、日本乳化剤株式会社製)など低級アルコールにPO付加を行い精密蒸留された市販原料を使用することもできる。精密蒸留等により実質的に分布を持たない単一付加モル数のものにすると特に浸透力が優れたものとなるため好ましい。In this case, the narrow ratio when the narrow ratio is calculated according to the formula (A) for the intermediate 1 is preferably 40% by mass or more from the viewpoint of penetrating power and liquid stability, and more preferably 50% by mass or more. 55 mass% or more is particularly preferable. Further, the remaining amount of the unreacted raw material alcohol is preferably 2.5% by mass or less in the total fatty acid polyoxyalkylene alkyl ether from the viewpoint of penetrating power and liquid stability, and 1.0% by mass or less. More preferred.
Such a PO adduct having a high narrow ratio is not particularly limited, and it is precise by adding PO to a lower alcohol such as tripropylene glycol monomethyl ether (for example, trade name methylpropylene triglycol (MFTG), manufactured by Nippon Emulsifier Co., Ltd.). Distilled commercial raw materials can also be used. It is preferable to use a single added mole number having substantially no distribution by precision distillation or the like because the penetrating power is particularly excellent.
さらに得られた狭い付加モル数分布を有する中間体1にEOを付加重合してブロック付加体(中間体2)を得た場合、この中間体2からさらに蒸留等によりEOが付加しなかった残存中間体1やEOの低付加モル体を除去して、よりEO付加モル数分布をシャープなものとすることで起泡力、破泡性が良好となり、さらに水と低級アルコールなどの溶剤と混合して製剤化したときに、製剤の低温安定性に優れたものとなり、不均一化や析出、固化などが抑制される。中間体2から蒸留により低付加モル体などの除去は、減圧蒸留など常法により行うことができる。また、前記製造方法により得られたもの、1種又は2種以上を適宜混合して製造し、使用してもよい。 Further, when EO was subjected to addition polymerization to the obtained intermediate 1 having a narrow addition mole number distribution to obtain a block adduct (intermediate 2), EO was not further added from the intermediate 2 by distillation or the like. By removing the intermediate 1 and low-addition moles of EO, the EO addition mole number distribution becomes sharper, and the foaming power and foam-breaking property are improved, and further mixed with a solvent such as water and a lower alcohol. When formulated into a formulation, the formulation is excellent in low-temperature stability, and unevenness, precipitation, solidification, and the like are suppressed. Removal of low addition moles and the like from intermediate 2 by distillation can be performed by a conventional method such as vacuum distillation. Moreover, what was obtained by the said manufacturing method, 1 type (s) or 2 or more types may be mixed, manufactured, and used.
前記脂肪酸ポリオキシアルキレンアルキルエーテルの製造方法として、前記R2Oに相当する低級アルコールに対して、同様に前記複合金属酸化物触媒を用いてブロック付加重合(特開平9−262456号公報参照)した後に対応する脂肪酸エステルとエステル交換あるいは対応する脂肪酸とエステル化を行う方法や、さらには前記低級アルコールにアルカリ触媒を用いてPOとEOをブロック付加重合を行い、その後に適宜未反応の低級アルコールや低付加モル数成分を蒸留除去することで所望のナロー率となるように付加モル数分布を制御し、その後に対応する脂肪酸エステルとエステル交換あるいは対応する脂肪酸とエステル化を行う方法などが挙げられるが、脂肪酸エステルとエステル交換あるいは対応する脂肪酸とエステル化するための触媒としては、特に制限はなく、水酸化リチウム、水酸化セシウム、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、水酸化バリウム、水酸化カルシウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、塩化リチウムや、ギ酸ナトリウム、ナトリウムメトキシド等の塩基性触媒が挙げられる。また、酸触媒としては、硫酸、硫酸ジルコニア、p−トルエンスルホン酸(p−TS)、ベンゼンスルホン酸(BS)、2,4−ジメチルベンゼンスルホン酸(2,4−DMBS)、無機酸化触媒としては、ZrO2、TiO2、SiO2、PO4、Al2O3、ZnOが挙げられる。
常温エステル交換反応に用いる触媒としては、特に制限はなく、スズ化合物である、塩化ジアルキルスズ、酸化ジアルキルスズ、フルオロアルキルスズ、アミノプロピルスズが挙げられる。
その他では、チタン系のテトライソプロピルチタネート、テトラn−ブチルチタネート、テトラエタノールアミンチタネート、テトラステアリルチタネートなどが挙げられる。また、その他に、サマリウムヨージド、及びN−ヘテロサイクリックカルベンが挙げられる。また、ランタン(III)トリイソプロポキシド([La(Oi−Pr)3])、ランタン(III)トリストリフルオロメチルスルホニウム塩([La(OTf)3])、ランタントリスアセチルアセトネート、酢酸鉛、ナフテン酸鉛等の鉛化合物、リサージ、ナフテン酸カルシウム及び酵素が挙げられる。
前記農薬用界面活性剤組成物は、農薬原料として使用するため、チタン、スズが残存するのは好ましくないため、吸着処理またはろ過精製処理を行うのが好ましい。特に好ましくは、環境への影響の視点でエステル交換またはエステル化触媒として、水酸化ナトリウム、炭酸水素ナトリウム、またはナトリウムメトキシドを使用し、かつ吸着処理またはろ過精製処理を行うのがよい。
前記脂肪酸ポリオキシアルキレンアルキルエーテルを製造する際に脂肪酸メチルエステルなどの脂肪酸エステルとエステル交換により製造する場合、脂肪酸ポリオキシアルキレンアルキルエーテルに残存する脂肪酸エステル量は、液安定性、浸透力の点で3.0質量%以下が好ましく、2.0質量%以下がさらに好ましい。As a method for producing the fatty acid polyoxyalkylene alkyl ether, block addition polymerization was similarly performed on the lower alcohol corresponding to the R 2 O using the composite metal oxide catalyst (see JP-A-9-262456). Later, a method of transesterification with the corresponding fatty acid ester or esterification with the corresponding fatty acid, and further, block addition polymerization of PO and EO using an alkali catalyst for the lower alcohol, followed by the unreacted lower alcohol or Examples include a method in which the addition mole number distribution is controlled by distilling off the low addition mole number component so as to obtain a desired narrow ratio, followed by transesterification with the corresponding fatty acid ester or esterification with the corresponding fatty acid. Transesterified with fatty acid ester or esterified with corresponding fatty acid ester There are no particular restrictions on the catalyst for the lithium hydroxide, cesium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, Examples include basic catalysts such as lithium chloride, sodium formate, and sodium methoxide. Examples of the acid catalyst include sulfuric acid, zirconia sulfate, p-toluenesulfonic acid (p-TS), benzenesulfonic acid (BS), 2,4-dimethylbenzenesulfonic acid (2,4-DMBS), and inorganic oxidation catalyst. ZrO 2 , TiO 2 , SiO 2 , PO 4 , Al 2 O 3, ZnO.
There is no restriction | limiting in particular as a catalyst used for normal temperature transesterification reaction, Dialkyl tin chloride, dialkyl tin oxide, fluoroalkyl tin, and aminopropyl tin which are tin compounds are mentioned.
Other examples include titanium-based tetraisopropyl titanate, tetra-n-butyl titanate, tetraethanolamine titanate, and tetrastearyl titanate. Other examples include samarium iodide and N-heterocyclic carbene. In addition, lanthanum (III) triisopropoxide ([La (Oi-Pr) 3 ]), lanthanum (III) tristrifluoromethylsulfonium salt ([La (OTf) 3 ]), lanthanum trisacetylacetonate, lead acetate , Lead compounds such as lead naphthenate, resurge, calcium naphthenate and enzymes.
Since the surfactant composition for agricultural chemicals is used as a raw material for agricultural chemicals, it is not preferable that titanium and tin remain. Therefore, it is preferable to perform an adsorption treatment or a filtration purification treatment. Particularly preferably, sodium hydroxide, sodium bicarbonate, or sodium methoxide is used as a transesterification or esterification catalyst from the viewpoint of environmental impact, and an adsorption treatment or a filtration purification treatment is performed.
When the fatty acid polyoxyalkylene alkyl ether is produced by transesterification with a fatty acid ester such as a fatty acid methyl ester, the amount of fatty acid ester remaining in the fatty acid polyoxyalkylene alkyl ether is in terms of liquid stability and penetrating power. 3.0 mass% or less is preferable and 2.0 mass% or less is more preferable.
前記農薬用界面活性剤組成物は、農薬活性成分を含有する農薬製剤の展着剤や、農薬活性成分等の分散剤、可溶化剤として、液状物である農薬製剤中に配合されて、あるいは、農薬用展着剤として液状の農薬製剤とともに用いられることに適する。 The agrochemical surfactant composition is blended in a liquid agrochemical formulation as a spreading agent for agrochemical formulations containing an agrochemical active ingredient, a dispersant for an agrochemical active ingredient, or a solubilizer, or Suitable for use with liquid agricultural chemical formulations as spreading agent for agricultural chemicals.
例えば、本発明の農薬用界面活性剤組成物を農薬用展着剤として使用する場合、通常、農薬の散布時に薬液に混合して使用される。使用濃度は一般に水などで希釈し30ppm〜5,000ppm程度であり、農薬の種類や対象植物が濡れやすい植物か濡れにくい植物かによって適宜調整して用いる。 For example, when the surfactant composition for agricultural chemicals of the present invention is used as a spreading agent for agricultural chemicals, it is usually used by mixing with a chemical solution at the time of spraying agricultural chemicals. The concentration used is generally about 30 ppm to 5,000 ppm diluted with water or the like, and is used by appropriately adjusting depending on the type of agricultural chemical and whether the target plant is a wet or difficult wet plant.
前記農薬用界面活性剤組成物を農薬用展着剤として使用する場合、前記脂肪酸ポリオキシアルキレンアルキルエーテルは水に溶解しづらいため、界面活性剤と水と溶剤との混合液として使用するのが好ましい。
前記溶剤としては、前記脂肪酸ポリオキシアルキレンアルキルエーテルを容易に溶解しかつ水と容易に混合する点で、低級アルコールやグリコール類が挙げられる。
本明細書において、前記低級アルコールとは、炭素数1〜4のアルコールを示す。
前記低級アルコールとしては、特に制限はなく、目的に応じて適宜選択することができ、例えば、メタノール、エタノール、イソプロピルアルコール、n−プロピルアルコール、イソブチルアルコール、n−ブチルアルコールが挙げられる。
前記グリコール類としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、エチレングリコール、プロピレングリコールが挙げられる。また、アセトン、炭酸プロピレン、N−メチルピロリドン、γ−ブチロラクトンなどもよい。農薬用展着剤として環境に放出される点で、好ましくはエタノール、イソプロピルアルコール、イソブチルアルコールがよい。特に好ましくは引火点が高く安全性が向上する点でイソプロピルアルコール、イソブチルアルコールがよい。
前記農薬用界面活性剤組成物を農薬用展着剤として使用する場合、前記農薬用界面活性剤組成物における、界面活性剤としての前記脂肪酸ポリオキシアルキレンアルキルエーテルの含有量の比率としては、10質量%〜60質量%であり、20質量%〜40質量%が好ましく、前記水の含有量の比率としては、10質量%〜70質量%であり、20質量%〜60質量%が好ましく、前記低級アルコールの含有量の比率としては、10質量%〜70質量%であり、20質量%〜50質量%が好ましい。また、前記低級アルコールに代えて、同比率の前記グリコール類及び前記低級アルコールと前記グリコール類との混合液からなる溶媒を用いることもできる。
前記農薬用展着剤として使用する場合の前記農薬用界面活性剤組成物の具体的な組成例としては、前記脂肪酸ポリオキシアルキレンアルキルエーテルの界面活性剤/水/イソプロピルアルコール=30質量%/30質量%/40質量%が低温安定性に優れていてよい。
その他に、カルボキシメチルセルロース、アラビアゴム、カゼイン等の固着剤、ナフタレンスルホン酸ホルムアルデヒド縮合物、リグニンスルホン酸塩等の分散剤等を適宜含有することができる。When the surfactant composition for agricultural chemicals is used as a spreading agent for agricultural chemicals, the fatty acid polyoxyalkylene alkyl ether is difficult to dissolve in water. Therefore, the fatty acid polyoxyalkylene alkyl ether should be used as a mixture of a surfactant, water and a solvent. preferable.
Examples of the solvent include lower alcohols and glycols in that the fatty acid polyoxyalkylene alkyl ether can be easily dissolved and easily mixed with water.
In the present specification, the lower alcohol represents an alcohol having 1 to 4 carbon atoms.
There is no restriction | limiting in particular as said lower alcohol, According to the objective, it can select suitably, For example, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol is mentioned.
There is no restriction | limiting in particular as said glycols, According to the objective, it can select suitably, For example, ethylene glycol and propylene glycol are mentioned. Further, acetone, propylene carbonate, N-methylpyrrolidone, γ-butyrolactone, and the like may be used. Ethanol, isopropyl alcohol, and isobutyl alcohol are preferable because they are released to the environment as spreading agents for agricultural chemicals. In particular, isopropyl alcohol and isobutyl alcohol are preferable because they have a high flash point and improve safety.
In the case where the surfactant composition for agricultural chemicals is used as a spreading agent for agricultural chemicals, the content ratio of the fatty acid polyoxyalkylene alkyl ether as the surfactant in the surfactant composition for agricultural chemicals is 10 20% by mass to 40% by mass is preferable, and the water content ratio is 10% by mass to 70% by mass, preferably 20% by mass to 60% by mass, As a ratio of content of a lower alcohol, they are 10 mass%-70 mass%, and 20 mass%-50 mass% are preferable. Moreover, it can replace with the said lower alcohol and the solvent which consists of the liquid mixture of the said glycols and the said lower alcohol and the said glycols of the same ratio can also be used.
As a specific composition example of the surfactant composition for agricultural chemicals when used as the spreading agent for agricultural chemicals, the surfactant of fatty acid polyoxyalkylene alkyl ether / water / isopropyl alcohol = 30% by mass / 30 % By mass / 40% by mass may be excellent in low-temperature stability.
In addition, a fixing agent such as carboxymethyl cellulose, gum arabic, and casein, a dispersant such as naphthalenesulfonic acid formaldehyde condensate, and lignin sulfonate can be appropriately contained.
前記農薬用界面活性剤組成物は農薬用活性剤として、機能性添着剤(アジュバンド)、水和剤、乳化剤、分散及び可溶化剤等に使用することができる。また、殺菌剤、殺虫剤、殺ダニ剤、除草剤及び植物成長調節剤等の農薬を使用するための界面活性剤として使用することができる。
また、農薬製剤の分散、可溶化剤として使用する場合、農薬薬効成分によって異なるが、界面活性剤として5質量%〜50質量%程度用いることができる。The agrochemical surfactant composition can be used as an agrochemical active agent in functional additives (adjubands), wettable powders, emulsifiers, dispersions, and solubilizers. Moreover, it can be used as a surfactant for using agricultural chemicals such as fungicides, insecticides, acaricides, herbicides and plant growth regulators.
Moreover, when using as a dispersion | distribution and solubilizer of an agrochemical formulation, although it changes with agricultural chemical medicinal ingredients, about 5 mass%-50 mass% can be used as surfactant.
本発明によれば、上記のように水、低級アルコールなどの溶剤と混合した製剤としたときに低泡性で泡の破泡性などに優れるとともに、低温安定性に優れ、分離(不均一化)、析出、固化などの発生が抑制され、農薬用の展着剤や、農薬製剤用の分散、可溶化剤としての使用に適する取り扱い性の良好な界面活性剤組成物を得ることができる。
また、農薬分野に使用できる環境安全性に優れる界面活性剤組成物であるため、その他環境に放出される土木、エネルギー分野等での界面活性剤として使用することも可能である。According to the present invention, when the preparation is mixed with a solvent such as water or a lower alcohol as described above, it has low foaming properties and excellent foam breaking properties, and has excellent low-temperature stability and separation (non-uniformization). ), The occurrence of precipitation, solidification, etc. is suppressed, and a surfactant composition with good handleability suitable for use as a spreading agent for agricultural chemicals, a dispersion for agricultural chemical formulations, and a solubilizing agent can be obtained.
Moreover, since it is a surfactant composition excellent in environmental safety that can be used in the agricultural chemical field, it can also be used as a surfactant in other civil engineering and energy fields that are released to the environment.
以下に実施例を用いて本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。実施例で用いた評価方法、分析方法を以下に示す。 Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. The evaluation methods and analysis methods used in the examples are shown below.
(1)評価方法
(i)起泡力及び破泡性
1000mLのメスシリンダーに有効成分濃度1,000ppmの試験液を100mL入れ、この水溶液にガラスボールフィルター(木下理化工業株式会社製、フィルター粒子No.4(5〜10μm))を用いて、底部より窒素ガスを1,000mL/minで3分間吹き込み、吹き込み終了直後の泡の高さを測定し、起泡力とした。また次の式により、吹き込み終了直後の泡の高さと吹き込み終了から5分後の泡の高さから破泡性を求めた。
破泡性(%)=(直後の泡の高さ−5分後の泡の高さ)/直後の泡の高さ×100(1) Evaluation method (i) Foaming force and foam breaking property 100 mL of a test solution having an active ingredient concentration of 1,000 ppm is placed in a 1000 mL measuring cylinder, and a glass ball filter (manufactured by Kinoshita Rika Kogyo Co., Ltd., filter particle No.) is added to this aqueous solution. .4 (5 to 10 μm)), nitrogen gas was blown from the bottom at 1,000 mL / min for 3 minutes, and the height of the foam immediately after the completion of blowing was measured to determine the foaming power. Moreover, the foam breaking property was calculated | required from the height of the foam immediately after completion | finish of blowing, and the height of the foam 5 minutes after the completion of blowing by the following formula.
Foam breakability (%) = (height of foam immediately after -5 height of foam after 5 minutes) / height of foam immediately after × 100
前記起泡力と破泡性とは、以下の判定基準で評価を行った。
<起泡力の判定基準(泡高)>
0mm以上90mm未満:○
90mm以上120mm未満:△
120mm以上:×
<破泡性の判定基準>
70%以上:○
40%以上70%未満:△
40%未満:×The foaming power and foam breaking property were evaluated according to the following criteria.
<Criteria for foaming power (bubble height)>
0 mm or more and less than 90 mm: ○
90 mm or more and less than 120 mm: △
120 mm or more: ×
<Judgment criteria for foam breaking property>
70% or more: ○
40% or more and less than 70%: △
Less than 40%: ×
(ii)浸透力(ぬれ性)
ドレーブス(Draves)法に準じて行った。ウールニットの縦20cm×横3cmの布片を切り出し、試験布とした。1,000mLメスシリンダーにおいて、針金アンカー部が底部にくるような針金製器具を作成し、針金アンカー部と蛇ピンフック(約0.1g)をナイロン糸(約3cm)でつないだ。各界面活性剤試料を3度硬水で30ppmに希釈した試験液を1000mLメスシリンダーに入れた。蛇ピンフックに試験布の一端を掛け、針金アンカー部が底部にくるように試験液の入った1,000mLメスシリンダーに沈め、試験布が液中で浮遊した状態とした。入れた時から蛇ピンフックが沈みはじめる瞬間(フックとアンカーの間の糸がゆるんだとき)までの時間を計った。時間が短いほど浸透力は良好であり、30秒未満を合格、30秒以上を不合格とした。(Ii) Penetration power (wetting)
This was performed according to the Draves method. A piece of wool knit 20 cm long x 3 cm wide was cut out and used as a test cloth. In a 1,000 mL graduated cylinder, a wire instrument was prepared such that the wire anchor part was at the bottom, and the wire anchor part and the snake pin hook (about 0.1 g) were connected with a nylon thread (about 3 cm). A test solution obtained by diluting each surfactant sample to 30 ppm with 3 degree hard water was placed in a 1000 mL graduated cylinder. One end of the test cloth was hung on the snake pin hook and submerged in a 1,000 mL graduated cylinder containing the test solution so that the wire anchor part was at the bottom, so that the test cloth was suspended in the liquid. The time from when it was put to the moment when the snake pin hook began to sink (when the thread between the hook and anchor loosened) was measured. The shorter the time, the better the penetrating power, with less than 30 seconds passed and 30 seconds or longer rejected.
(iii)液安定性試験
界面活性剤試料/イオン交換水/イソプロピルアルコール=30/30/40(質量部)の溶液を作成し、均一状態になるまで攪拌した後、サンプル瓶に密閉し、温度−5℃に設定した恒温槽内に72時間置いた。保存期間後に目視確認し、−5℃で均一な溶液状を保つものを◎、析出物や液分離が発生しても、20℃まで昇温したときに均一液状に復元するものを○、析出物や液分離が解消されないものは×とした。(Iii) Liquid stability test A solution of surfactant sample / ion-exchanged water / isopropyl alcohol = 30/30/40 (parts by mass) was prepared, stirred until uniform, then sealed in a sample bottle, and the temperature It was placed in a thermostatic bath set at −5 ° C. for 72 hours. Visually confirmed after the storage period, ◎ that maintains a uniform solution at -5 ° C, ◎, even if precipitates or liquid separation occurs, ○ that precipitates back to a uniform liquid when heated to 20 ° C, precipitated The thing which cannot cancel a thing and liquid separation was set as x.
(iv)可溶化力
試験液として各界面活性剤試料の濃度1,000ppmの水溶液を作成し、この試験液4mlに対して被可溶化物として油溶性色素YellowOBを40mg加え、室温で24時間振とうした。その後0.45μmの前処理用フィルター(GLサイエンス製クロマトディスク、13N、非水系、未滅菌)でろ過し、等量のエタノールを加え、450nmの吸収を測定した。可溶化量としては、30ppm以上を合格、30ppm未満を不合格とした。(Iv) Solubilizing power An aqueous solution having a concentration of 1,000 ppm of each surfactant sample was prepared as a test solution, 40 mg of oil-soluble dye YellowOB was added as a solubilized product to 4 ml of this test solution, and the mixture was shaken at room temperature for 24 hours. That ’s it. Thereafter, the solution was filtered through a 0.45 μm pretreatment filter (GL Science Chromatodisc, 13N, non-aqueous, non-sterile), an equal amount of ethanol was added, and the absorption at 450 nm was measured. As the solubilization amount, 30 ppm or more was accepted and less than 30 ppm was rejected.
(v)生分解性
化審法、微生物等による化学物質の分解度試験に準拠した。すなわち、試料濃度100ppmの試験液中に、固形分として30ppmの活性汚泥を植種源として添加し、BOD(生物化学的酸素消費量)、TOD(総酸素消費量)を経日で測定し、生分解度=BOD/TOD(%)から以下の基準で評価する。
○:28日以内に生分解度60%に達する
×:生分解度60%に達するまで29日以上必要、または一定量分解し、それ以上分解しない(V) Biodegradability It complied with the Chemical Substances Control Law and chemical substance degradation test by microorganisms. That is, in a test solution having a sample concentration of 100 ppm, activated sludge having a solid content of 30 ppm is added as a seeding source, and BOD (biochemical oxygen consumption) and TOD (total oxygen consumption) are measured over time. Biodegradability = BOD / TOD (%) is evaluated according to the following criteria.
○: Biodegradation reaches 60% within 28 days ×: Necessary for 29 days or more until biodegradation reaches 60%, or decomposes a certain amount, does not further decompose
(vi)魚毒性
JIS K 0102工場排水試験法71.魚類による急性毒性試験に準拠し、ヒメダカの魚毒性TLm値(48時間)、すなわち48時間後における半数致死濃度(ppm)を測定した。100ppm以上を合格、100ppm未満を不合格とした。(Vi) Fish toxicity JIS K 0102 factory drainage test method 71. Based on an acute toxicity test with fish, the fish toxicity TLm value (48 hours) of medaka, ie, the half-lethal concentration (ppm) after 48 hours, was measured. 100 ppm or more was accepted and less than 100 ppm was rejected.
(vii)植物薬害性
キャベツ、スナックエンドウに展着剤の有効成分として5,000ppm散布し、5日後の薬害発生率(%)を調べた。薬害発生率がいずれも30%未満を合格、30%以上を不合格とした。(Vii) Plant phytotoxicity 5,000 ppm was spread as an active ingredient of a spreading agent on cabbage and snack peas, and the incidence of phytotoxicity (%) after 5 days was examined. In all cases, the incidence of phytotoxicity was less than 30%, and 30% or more was rejected.
(3)分析方法
以下に分析方法について述べる。EO、POの平均付加モル数は、原料及びアルキレンオキシドの仕込みの質量の収支から計算で求めた。ただし、EO、POの付加反応後に蒸留を行った場合には、以下(i)の1H−NMR分析により平均付加モル数を求めた。
(i)平均付加モル数の算出方法
得られた化合物30mgを4mLの重クロロホルムに溶解し、1H−NMR(300MHz、日本電子株式会社製 FT NMR SYSTEM JNM−LA300)にて測定した。重クロロホルムのケミカルシフトを7.30ppm基準として、ケミカルシフト0.87ppm(脂肪酸の末端メチル)、1.13ppm〜1.15ppm(POの側鎖メチル)、3.32ppm〜3.66ppm(POのメチンとメチレン)、3.52ppm〜3.71ppm(EOのメチレン)の各ピークの積分値比率から計算で求めた。
(ii)EO・PO付加モル数分布の測定及びナロー率の算出方法
目的物及び中間体のEO・POの付加モル数分布は下記により行った。
装置条件 ガスクロマトグラム:HP−6890 Mass Selective Detector(GC−MS)、検出器:FID
カラム:UltraALLOYPY−1、φ0.25mm×長さ30m、膜厚0.25μm
分析条件 Injection:380℃、Detecter:380℃
初期:50℃→360℃(20min)、昇温:10℃/min、キャリアガス:He
スプリット比:50対1
試料0.5gをアセトン10gに溶解し、1μL注入、各EO(PO)付加モル数毎の濃度(%)を測定した。得られたクロマトグラムの最大ピークと、その前後2モル体(合計5モル付加体)の合計をナロー率とした。
(iii)中間体1、2に含まれる未反応脂肪酸メチル及び未反応メタノールの定量
(1)未反応脂肪酸メチルの場合
内部標準としてラウリン酸メチルを0.06gと試料を2gとり、アセトン4gに溶解し、2μL注入。ラウリン酸メチルの濃度を変更した際のピーク面積と内部標準物質のピーク面積から検量線を作成し、試料中に含まれる未反応物の定量を行った。
(2)未反応メタノールの場合
溶媒による希釈をせずに、試料をそのまま1μL注入し、得られたクロマトグラムの面積%から、未反応メタノール量を算出した。
<装置条件>
ガスクロマトグラム:島津GC−14A、検出器:FID、カラム:ガラス製φ3mm×1m、充填剤:2%silicon OV−1(60/80mesh)
−共通条件−
Injection:320℃、Detecter:320℃、N2:50mL/min、H2:0.75kg/cm2、Air:0.5kg/cm2
−未反応メチルエステルの場合−
初期:100℃→230℃(昇温:10℃/min)→320℃(昇温:30℃/min)、22min保持
−未反応メタノールの場合−
初期:50℃→320℃(20min保持)、昇温:10℃/min(3) Analysis method The analysis method is described below. The average added mole number of EO and PO was calculated from the balance of the mass of the raw materials and the charged amount of alkylene oxide. However, when distillation was performed after the addition reaction of EO and PO, the average number of moles added was determined by 1 H-NMR analysis of (i) below.
(I) dissolving the compound 30mg of calculation method obtained the average addition mole number deuterochloroform 4 mL, was measured by 1 H-NMR (300MHz, JEOL Ltd. FT NMR SYSTEM JNM-LA300). Chemical shift 0.87 ppm (fatty acid terminal methyl), 1.13 ppm to 1.15 ppm (PO side chain methyl), 3.32 ppm to 3.66 ppm (PO methine, based on 7.30 ppm as the chemical shift of deuterated chloroform And methylene) and 3.52 ppm to 3.71 ppm (methylene of EO).
(Ii) Measurement of EO / PO addition mole number distribution and calculation method of narrow ratio The addition mole number distribution of EO / PO of the target product and the intermediate was performed as follows.
Equipment conditions Gas chromatogram: HP-6890 Mass Selective Detector (GC-MS), Detector: FID
Column: UltraALLOYPY-1, φ0.25 mm × length 30 m, film thickness 0.25 μm
Analysis conditions Injection: 380 ° C., Detector: 380 ° C.
Initial: 50 ° C. → 360 ° C. (20 min), temperature rise: 10 ° C./min, carrier gas: He
Split ratio: 50 to 1
0.5 g of a sample was dissolved in 10 g of acetone, 1 μL was injected, and the concentration (%) for each EO (PO) added mole number was measured. The sum of the maximum peak of the obtained chromatogram and the two moles before and after that (total 5 mole adduct) was defined as the narrow ratio.
(Iii) Determination of unreacted fatty acid methyl and unreacted methanol contained in intermediates 1 and 2 (1) In the case of unreacted fatty acid methyl 0.06 g of methyl laurate and 2 g of sample were taken as internal standards and dissolved in 4 g of acetone. 2 μL injection. A calibration curve was created from the peak area when the concentration of methyl laurate was changed and the peak area of the internal standard substance, and unreacted substances contained in the sample were quantified.
(2) In the case of unreacted methanol 1 μL of the sample was injected as it was without dilution with a solvent, and the amount of unreacted methanol was calculated from the area% of the obtained chromatogram.
<Device conditions>
Gas chromatogram: Shimadzu GC-14A, detector: FID, column: glass φ3 mm × 1 m, filler: 2% silicon OV-1 (60/80 mesh)
-Common conditions-
Injection: 320 ° C., Detector: 320 ° C., N 2 : 50 mL / min, H 2 : 0.75 kg / cm 2 , Air: 0.5 kg / cm 2
-In case of unreacted methyl ester-
Initial: 100 ° C. → 230 ° C. (temperature increase: 10 ° C./min)→320° C. (temperature increase: 30 ° C./min), 22 min hold-in the case of unreacted methanol—
Initial: 50 ° C. → 320 ° C. (20 min hold), temperature rise: 10 ° C./min
(実施例1)
2.5MgO・Al2O3・nH2Oなる化学式を持つアルミナ・マグネシア複合酸化物(協和化学工業株式会社製キョーワード300)を窒素気流下、750℃で3時間焼成し、焼成アルミナ・マグネシア複合酸化物(Al/Mgモル比=0.44/0.56)触媒を得た。4Lオートクレーブに、オレイン酸メチル(パーム油由来の炭素数18留分由来の脂肪酸メチルエステル、商品名パステルM182、ライオン株式会社製、ヨウ素価91)1,073gと、得られた触媒5gとともに触媒改質剤として40%KOHを0.58g仕込み、窒素置換を2度行った。
その後180℃まで昇温して、窒素により反応缶内を常圧に戻し、PO628g(オレイン酸メチル1モルに対して3モル相当)を徐々に容器内へ導入した。導入終了直後、0.48MPaであった圧力が反応進行とともに低下し、2時間後に圧力0.22MPaで一定となるまでPO付加反応を継続して行った。得られた中間体1Aを一部サンプリングし、ガスクロマトグラフィーにより分析した結果、未反応脂肪酸メチルが12.8質量%含まれていた。
次いで、同様に窒素置換、昇温後EO794g(オレイン酸メチル1モルに対して5モル相当)を徐々に容器内へ導入した。導入終了直後、0.5MPaであった圧力が反応進行とともに低下し、0.5時間後に圧力0.24MPaで一定となるまでEO付加反応を継続して行い、得られた反応物は珪藻土を用いてろ過処理し目的物を得た。PO、EOのブロック付加反応により得られた化合物1Aの未反応脂肪酸メチルは1.1質量%であった。測定結果及び評価結果を表1、2に示す。Example 1
Alumina-magnesia composite oxide (KYOWARD 300 manufactured by Kyowa Chemical Industry Co., Ltd.) having a chemical formula of 2.5 MgO.Al 2 O 3 .nH 2 O was calcined at 750 ° C. for 3 hours in a nitrogen stream, and calcined alumina-magnesia A composite oxide (Al / Mg molar ratio = 0.44 / 0.56) catalyst was obtained. Into a 4 L autoclave, 1073 g of methyl oleate (fatty acid methyl ester derived from palm oil derived from carbon number 18 fraction, trade name: Pastel M182, manufactured by Lion Co., Ltd., iodine number 91) and 5 g of the obtained catalyst were modified. As a quality agent, 0.58 g of 40% KOH was charged, and nitrogen substitution was performed twice.
Thereafter, the temperature was raised to 180 ° C., the inside of the reaction vessel was returned to normal pressure with nitrogen, and PO 628 g (corresponding to 3 mol per 1 mol of methyl oleate) was gradually introduced into the vessel. Immediately after the introduction, the pressure of 0.48 MPa decreased with the progress of the reaction, and the PO addition reaction was continued until the pressure became constant at 0.22 MPa after 2 hours. A part of the obtained intermediate 1A was sampled and analyzed by gas chromatography. As a result, 12.8% by mass of unreacted fatty acid methyl was contained.
Subsequently, similarly, after nitrogen substitution and heating, 794 g of EO (corresponding to 5 mol with respect to 1 mol of methyl oleate) was gradually introduced into the container. Immediately after the introduction, the pressure that was 0.5 MPa decreased with the progress of the reaction, and after 0.5 hours, the EO addition reaction was continued until the pressure became constant at 0.24 MPa, and the obtained reaction product used diatomaceous earth. The target product was obtained by filtration. The unreacted fatty acid methyl of compound 1A obtained by the block addition reaction of PO and EO was 1.1% by mass. Tables 1 and 2 show the measurement results and the evaluation results.
(実施例2)
POの添加量を565g(オレイン酸メチル1モルに対して2.7モル相当)とし、さらに、得られた中間体1Bに対して、中間体1Bに含まれる未反応メチルエステルを除去するため、175℃から200℃まで段階的に昇温しつつ、10Torr以下まで減圧蒸留を行ったこと以外は、実施例1と同様にして、PO、EOのブロック付加反応を行い化合物1Bを得た。減圧蒸留後の中間体1B中の未反応の原料脂肪酸メチルの量は0.8質量%であり、さらにEO付加を行った結果得られた化合物1B中の未反応脂肪酸メチルが0.3質量%であった。測定結果及び評価結果を表1、2に示す。(Example 2)
The amount of PO added was 565 g (equivalent to 2.7 mol per 1 mol of methyl oleate), and the unreacted methyl ester contained in the intermediate 1B was removed from the obtained intermediate 1B. Compound 1B was obtained by carrying out a block addition reaction of PO and EO in the same manner as in Example 1 except that vacuum distillation was performed to 10 Torr or less while the temperature was raised stepwise from 175 ° C. to 200 ° C. The amount of unreacted starting fatty acid methyl in intermediate 1B after distillation under reduced pressure is 0.8% by mass, and the unreacted fatty acid methyl in compound 1B obtained as a result of EO addition is 0.3% by mass. Met. Tables 1 and 2 show the measurement results and the evaluation results.
(実施例3)
触媒改質剤として、40%KOHを添加しなかったこと以外は、実施例2と同様にして、PO、EOのブロック付加反応を行い化合物1Cを得た。減圧蒸留後の中間体1C中の未反応の原料脂肪酸メチルの量は1.8質量%であり、さらにEO付加を行った結果得られた化合物1C中の未反応脂肪酸メチルが1.6質量%であった。測定結果及び評価結果を表1、2に示す。(Example 3)
Compound 1C was obtained by performing a block addition reaction of PO and EO in the same manner as in Example 2 except that 40% KOH was not added as a catalyst modifier. The amount of unreacted raw material fatty acid methyl in intermediate 1C after distillation under reduced pressure is 1.8% by mass, and the unreacted fatty acid methyl in compound 1C obtained as a result of EO addition is 1.6% by mass. Met. Tables 1 and 2 show the measurement results and the evaluation results.
(比較例1)
EO794g(オレイン酸メチル1モルに対して5モル相当)とPO628g(オレイン酸メチル1モルに対して3モル相当)とを混合した状態で、徐々に容器内へ導入してEO、POランダム付加反応を行った以外は、実施例1と同様にして、目的物を得た。EO、POランダム付加反応は、導入終了直後、0.48MPaであった圧力が反応進行とともに低下し、2時間後に圧力0.24MPaで一定となるまで継続して行った。EO、POランダム付加反応により得られた化合物1Dの未反応脂肪酸メチルは1.2質量%であった。測定結果及び評価結果を表1、2に示す。(Comparative Example 1)
EO794g (equivalent to 5 moles per mole of methyl oleate) and PO628g (equivalent to 3 moles per mole of methyl oleate) are mixed and gradually introduced into the container, and EO, PO random addition reaction The target product was obtained in the same manner as in Example 1 except that The EO, PO random addition reaction was continued until the pressure, which was 0.48 MPa, decreased with the progress of the reaction immediately after the introduction was completed, and became constant at a pressure of 0.24 MPa after 2 hours. The unreacted fatty acid methyl of compound 1D obtained by EO and PO random addition reaction was 1.2% by mass. Tables 1 and 2 show the measurement results and the evaluation results.
(比較例2)
ブロック付加をPO、EOの順に行うことに代えて、EO、POの順に逆に行ったこと以外は実施例1と同様にして、目的物を得た。得られたEO、POのブロック付加反応により得られた化合物1Eの未反応脂肪酸メチルは1.1質量%であった。測定結果及び評価結果を表1、2に示す。(Comparative Example 2)
A target product was obtained in the same manner as in Example 1 except that the block addition was performed in the order of PO and EO, and that the addition was performed in the reverse order of EO and PO. The unreacted fatty acid methyl of compound 1E obtained by the block addition reaction of EO and PO obtained was 1.1% by mass. Tables 1 and 2 show the measurement results and the evaluation results.
(比較例3)
触媒改質剤として、40%KOHを添加しなかったこと以外は、実施例1と同様にして、目的物を得た。PO、EOのブロック付加反応により得られた化合物1Fの未反応脂肪酸メチルは4.9質量%であった。測定結果及び評価結果を表1、2に示す。(Comparative Example 3)
A target product was obtained in the same manner as in Example 1 except that 40% KOH was not added as a catalyst modifier. The unreacted fatty acid methyl of the compound 1F obtained by the block addition reaction of PO and EO was 4.9% by mass. Tables 1 and 2 show the measurement results and the evaluation results.
(実施例4)
4Lオートクレーブに、メタノール(純正化学製)387gと、触媒としてNaOHを1gを仕込み、反応器内の窒素置換を2度行った。その後90℃まで昇温して、POを1,405g(メタノール1モルに対して2.0モル相当)導入して付加反応を行った。
反応終了後、常圧で75℃から100℃まで段階的に昇温し、残存メタノールが1%以下となるまで蒸留を行い、中間体2A1を得た。この中間体2A1のPOの平均付加モル数は2.4モルであった。さらに、中間体2A1を857gに対し、EOを881g(中間体2A1、1モルに対して4モル相当)を導入して付加反応を行った。反応終了後、175℃から220℃まで段階的に昇温しつつ、10Torrまで減圧し再度蒸留を行った。得られた中間体2A2を853g、オレイン酸メチル(パステルM182、ヨウ素価91)を614g(中間体2A2に対して1.03モル)、炭酸水素ナトリウム7.3gを攪拌翼付の反応器に仕込み、攪拌下、常圧から10Torrまで段階的に減圧しながら、60℃から210℃まで昇温してエステル交換反応を行った。反応により得られた化合物2A中の未反応脂肪酸メチルが1.6質量%であった。測定結果及び評価結果を表1、2に示す。Example 4
A 4 L autoclave was charged with 387 g of methanol (manufactured by Junsei) and 1 g of NaOH as a catalyst, and the inside of the reactor was purged with nitrogen twice. Thereafter, the temperature was raised to 90 ° C., and 1,405 g of PO (corresponding to 2.0 mol relative to 1 mol of methanol) was introduced to carry out an addition reaction.
After the completion of the reaction, the temperature was raised stepwise from 75 ° C. to 100 ° C. at atmospheric pressure, and distillation was performed until the residual methanol was 1% or less to obtain Intermediate 2A1. The average number of moles of PO added in this intermediate 2A1 was 2.4 moles. Further, 881 g of EO (corresponding to 4 moles relative to 1 mole of intermediate 2A1) was introduced to 857 g of intermediate 2A1, and an addition reaction was performed. After completion of the reaction, the pressure was reduced to 10 Torr while gradually increasing the temperature from 175 ° C. to 220 ° C., and distillation was performed again. 853 g of the obtained intermediate 2A2, 614 g of methyl oleate (Pastel M182, iodine value 91) (1.03 mol with respect to the intermediate 2A2), and 7.3 g of sodium hydrogen carbonate were charged into a reactor equipped with a stirring blade. While stirring, the temperature was increased from 60 ° C. to 210 ° C. while performing stepwise pressure reduction from normal pressure to 10 Torr, and the transesterification reaction was performed. Unreacted fatty acid methyl in compound 2A obtained by the reaction was 1.6% by mass. Tables 1 and 2 show the measurement results and the evaluation results.
(実施例5)
POの添加量を2,108g(メタノール1モルに対して3モル相当)とし、実施例4と同様にPO付加反応を行った。反応終了後、常圧で75℃から130℃まで段階的に昇温し、残存メタノール及びメタノール−1PO体が1%以下となるまで蒸留を行い、さらに段階的に5Torrまで減圧しながら175〜220℃まで段階的に昇温して減圧蒸留を行い留出液を採取し、高沸点のボトム分をカットした中間体2B1を得た。中間体2B1へのPOの平均付加モル数は3モルであった。
中間体2B1に対して実施例4と同様の方法でEO付加反応を行い、中間体2B2を得、さらに実施例4と同様にエステル交換工程を行い化合物2Bを得た。得られた化合物2B中の未反応脂肪酸メチルが1.6質量%であった。測定結果及び評価結果を表1、2に示す。(Example 5)
The amount of PO added was 2,108 g (corresponding to 3 mol per 1 mol of methanol), and the PO addition reaction was carried out in the same manner as in Example 4. After completion of the reaction, the temperature was raised stepwise from 75 ° C. to 130 ° C. at atmospheric pressure, distilled until the residual methanol and methanol-1PO form became 1% or less, and further reduced in steps to 175-220 while reducing the pressure to 5 Torr. The temperature was raised stepwise to 0 ° C. and distillation under reduced pressure was performed to collect a distillate, thereby obtaining an intermediate 2B1 in which the bottom portion having a high boiling point was cut. The average number of moles of PO added to the intermediate 2B1 was 3 moles.
Intermediate 2B1 was subjected to an EO addition reaction in the same manner as in Example 4 to obtain Intermediate 2B2, and further subjected to a transesterification step in the same manner as Example 4 to obtain Compound 2B. Unreacted fatty acid methyl in the obtained compound 2B was 1.6% by mass. Tables 1 and 2 show the measurement results and the evaluation results.
(実施例6)
POの導入量を1,686g(メタノール1モルに対して2.4モル相当)としてPO付加反応を行ったこと、PO付加反応終了後の蒸留を行わなかったこと以外は、実施例4と同様にして、PO、EOのブロック付加反応を行い中間体2C2を得、さらにエステル交換反応を行って化合物2Cを得た。
中間体2C1中の未反応メタノールの量は1.9質量%であり、得られた化合物2C中の未反応脂肪酸メチルが1.7質量%であった。測定結果及び評価結果を表1、2に示す。(Example 6)
The same as in Example 4 except that the PO addition amount was 1,686 g (corresponding to 2.4 mol per 1 mol of methanol) and that the PO addition reaction was performed and the distillation after the PO addition reaction was not performed. Then, a block addition reaction of PO and EO was performed to obtain an intermediate 2C2, and further a transesterification reaction was performed to obtain a compound 2C.
The amount of unreacted methanol in the intermediate 2C1 was 1.9% by mass, and the unreacted fatty acid methyl in the obtained compound 2C was 1.7% by mass. Tables 1 and 2 show the measurement results and the evaluation results.
(比較例4)
POの導入量を2,108g(メタノール1モルに対して3モル相当)としPO付加反応を行ったこと、EOの導入量を1,289g(メタノール1モルに対して5モル相当)としEO付加反応を行ったこと、EO付加反応後に減圧蒸留とを行わなかったこと以外は、実施例6と同様にして、化合物2Dを得た。中間体2D1中の未反応メタノールの量は10.3質量%であり、得られた化合物2D中の未反応脂肪酸メチルは1.6質量%であった。測定結果及び評価結果を表1、2に示す。(Comparative Example 4)
The PO addition reaction was carried out with a PO introduction amount of 2,108 g (equivalent to 3 moles per mole of methanol), and the EO addition amount was 1,289 g (equivalent to 5 moles per mole of methanol). Compound 2D was obtained in the same manner as in Example 6 except that the reaction was carried out and vacuum distillation was not carried out after the EO addition reaction. The amount of unreacted methanol in the intermediate 2D1 was 10.3% by mass, and the unreacted fatty acid methyl in the obtained compound 2D was 1.6% by mass. Tables 1 and 2 show the measurement results and the evaluation results.
なお、各実施例に使用したサンプルについては生分解性、魚毒性、植物薬害性について評価を行った結果、いずれも生分解性に優れ(評価:○)、魚毒性、植物薬害性試験結果も合格する環境安全性の高いものであることが確認された。
Claims (5)
複合金属酸化物触媒を用いて脂肪酸アルキルエステルにPOとEOをブロック付加重合させる工程と、Block addition polymerization of PO and EO to fatty acid alkyl ester using a composite metal oxide catalyst;
低級アルコールに複合金属酸化物触媒を用いてブロック重合した後に、対応する脂肪酸エステルとエステル交換あるいは対応する脂肪酸とエステル化を行う工程と、A step of subjecting a lower alcohol to a block polymerization using a composite metal oxide catalyst, followed by transesterification with a corresponding fatty acid ester or esterification with a corresponding fatty acid;
低級アルコールにアルカリ触媒を用いてPOとEOをブロック付加重合を行った後、未反応の低級アルコールや低付加モル数成分を蒸留除去し、対応する脂肪酸エステルとエステル交換あるいは対応する脂肪酸とエステル化を行う工程と、を含み、After block addition polymerization of PO and EO using a lower alcohol with an alkali catalyst, unreacted lower alcohol and low addition mole number components are removed by distillation and transesterification with the corresponding fatty acid ester or esterification with the corresponding fatty acid. Including the steps of:
前記農薬用界面活性剤組成物が、下記一般式(I)で表される脂肪酸ポリオキシアルキレンアルキルエーテルであって、下記式(A)で表されるナロー率が60質量%以上である脂肪酸ポリオキシアルキレンアルキルエーテルを含有することを特徴とする農薬用界面活性剤組成物の製造方法。The agrochemical surfactant composition is a fatty acid polyoxyalkylene alkyl ether represented by the following general formula (I), wherein the fatty acid polyoxyalkylene alkyl ether represented by the following formula (A) is 60% by mass or more. A method for producing a surfactant composition for agricultural chemicals, comprising an oxyalkylene alkyl ether.
中間生成物2を形成するために、中間生成物1にブロック付加重合によりEOを付加する工程と、Adding EO to the intermediate product 1 by block addition polymerization to form the intermediate product 2;
中間生成物3を形成するために、未反応の低級アルコールや低付加モル数成分を蒸留除去する工程と、A step of distilling off unreacted lower alcohol and low added mole number components to form intermediate product 3;
農薬用界面活性剤組成物を得るために、中間生成物3をエステルとエステル交換あるいは脂肪酸とエステル化を行う工程とを含む農薬用界面活性剤組成物の製造方法により製造され、In order to obtain a surfactant composition for agricultural chemicals, the intermediate product 3 is produced by a method for producing a surfactant composition for agricultural chemicals comprising a step of transesterification with an ester or esterification with a fatty acid,
前記農薬用界面活性剤組成物が、下記一般式(I)で表される脂肪酸ポリオキシアルキレンアルキルエーテルであって、下記式(A)で表されるナロー率が60質量%以上である脂肪酸ポリオキシアルキレンアルキルエーテルを含有することを特徴とする農薬用界面活性剤組成物。The agrochemical surfactant composition is a fatty acid polyoxyalkylene alkyl ether represented by the following general formula (I), wherein the fatty acid polyoxyalkylene alkyl ether represented by the following formula (A) is 60% by mass or more. A surfactant composition for agricultural chemicals comprising an oxyalkylene alkyl ether.
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